Silica compaction

Andesite Making tools Complex metal silicates (about 60% silica) Compact and tough chips easily... 

It must be concluded that the quantitative determination of micropore size is still an ambiguous problem new theories, models, mechanisms and simulations are still under study [56-58]. Therefore isotherm interpretations must be used carefully and can be considered as useful mainly for qualitative studies. No reliable method has been developed for the determination of the micropore size distribution. At present the most promising approach appears to be that of pre-adsorption linked with the use of various probe molecules of known size and shape [59-61]. For example, this approach has been applied successfully for silica compacts characterisation in [61] using spherical symmetrical inert molecules, such as neopentane and trimethylsiloxysilane [(CH3)3SiO]4Si with diameters of 6.5 and 11.5 A respectively. In general the limited availability of volatile probe molecules with diameters extending above 10 A puts a restriction on the applicability of this method. Furthermore effective pore sizes determined by this technique depend on the kinetic and thermodynamic properties of the... 

J. D.F. Ramsay, Nitrogen adsorption in microporous silica compacts. /. Collloid Interface ScL, 51 (1975) 205. 

J.D.F. Ramsay and R.G. Avery, Adsorption in silica compacts containing pores of molecular size, in Pore Structure and Properties of Materials, Part I, Proc. Int. S)onp. lUPAC, Academia Prague, 1973, pp. B37-B45. 

Adsorptive properties of porous silicas compacts of pyrogenic powders, 506, 507f precipitated silicas, 507-509 silica gels, 509, 510-512 zeolitic silicas, 512-514 Adsorptive properties of silicas, challenges for improvement, 505 Aerogel(s) definition, 7, 620 porosities, 379, 380 ... 

Data on adsorption of nitrogen in microporous silica compacts were obtained by Ramsay and Avery (165b). They plotted their data using the DKR equation (165c) ... 

Silica compacts with pores of molecular size were prepared by Ramsay and Avery... 

Ramsay and Avery [82] investigated nitrogen adsorption in microporous silica compacts for 10-2>x>10-4 and found that < 7 kJ moI-1 for loose powder and increased with compaction and decrease in pore size. They found close agreement between amount adsorbed at monolayer coverage and intercept volume using the D-K equation, which indicated surface coverage as opposed to volume filling. 

Previous studies (refs. 1,2) of fumed silica compaction have established an empirical equation of state" between powder pore volume and applied pressure. 

The method may be illustrated by reference to a study of the effect of compaction of a non-porous powder. The nitrogen isotherm on a silica... 

Fig. 230 Adsorption of nitrogen at 77 K on a silica powder a) adsorption isotherms b) /-plot. Broken line, uncompacted powder continuous line, power compacted at 2-00 x 10 N m (130 ton in ). (—>—) adsorption (—<-) desorption. / is the ratio of the amount adsorbed on the powder to the amount adsorbed on the compact at the same relative...

Examples are provided by the work of Carman and Raal with CF2CI2 on silica powder, of Zwietering" with nitrogen on silica spherules and of Kiselev" with hexane on carbon black and more recently of Gregg and Langford with nitrogen on alumina spherules compacted at a series of pressures. In all cases, a well defined Type II isotherm obtained with the loose powder became an equally well defined Type IV isotherm with the compact moreover both branches of the hysteresis loop were situated (drove the isotherm for the uncompacted powder, but the pre-hysteresis region was scarcely affected (cf. Fig. 3.4). The results of all these and similar... 

Fig. 3.20 Pore size distributions (calculated by the Roberts method) for silica powder compacted at (A) Ibtonin" (B) 64tonin (C) 130 ton in". The distributions in (a) were calculated from the desorption brunch of the isotherms of nitrogen, and in (h) from the adsorption branch.

The evidence obtained in compaction experiments is of particular interest in the present context. Figure 3.22 shows the results obtained by Avery and Ramsay for the isotherms of nitrogen on compacts of silica powder. The hysteresis loop moved progressively to the left as the compacting pressure increased, but the lower closure point did not fall below a relative pressure of 0-40. Similar results were obtained in the compaction of zirconia powder both by Avery and Ramsay (cf. Fig. 4.5), and by Gregg and Langford, where the lower closure point moved down to 0-42-0-45p° but not below. With a mesoporous magnesia (prepared by thermal decomposition of the hydrated carbonate) the position of the closure point... 

Fig. 3.22 Adsorption isotherms of nitrogen at 77 K on silica powder and its compacts. (A) uncompressed (B) 10 ton in (C) 40 ton in" (D) 50 ton in (E) 100 ton in . Open symbols represent adsorption, solid symbols desorption. (Courtesy Ramsay.)...

Figure 3.26(a) and (h) gives results for nitrogen on a compact of silica. Curve (a) is a comparison plot in which the adsorption on the compact (ordinates) is plotted against that on the uncompacted powder (abscissae) there is a clear break followed by an increased slope, denoting enhanced adsorption on the compact, at p/p° = 0-15, far below the lower closure point ( 0-42) of the hysteresis loop in the isotherm (curve (b)). A second compact, prepared at 64 ton in" rather than 130 ton in", showed a break, not quite so sharp, at p/p° = 0-35. 

Fig. 3.26 Comparison plots for compacts of silica and magnesia. In each case the adsorption of nitrogen at 78 K on the compact is plotted against that on the uncompacted powder, (a) and (b), comparison plot and adsorption isotherm for silica powder compacted at 130 ton in (c) and (d), comparison plot and adsorption isotherm for precipitated magnesia compacted at 10 ton in. Note that the upward sweep of the comparison plot commences at a relative pressure below the inception of the loop.

The discrepancy between the pore area or the core area on the one hand and the BET area on the other is proportionately larger with silica than with alumina, particularly at the higher degrees of compaction. The fact that silica is a softer material than alumina, and the marked reduction In the BET area of the compact as compared with that of the loose material, indicates a considerable distortion of the particles, with consequent departure of the pore shape from the ideal of interstices between spheres. The factor R for cylinders (p. 171), used in the conversion to pore area in the absence of a better alternative, is therefore at best a crude approximation. 

Experimental findings in the intervening years have tended to support and extend this concept. The results obtained by Ramsay and Avery in their studies of the effect of compaction on the nitrogen isotherms of two finely divided powders, one of zirconia and the other of silica, are especially instructive in the present context. As in earlier studies (cf. Chapter 3) the isotherm on the original powder was of Type II, but on compaction it first became Type IV with a well defined hysteresis loop, which moved... 

As pointed out earlier (Section 3.5), certain shapes of hysteresis loops are associated with specific pore structures. Thus, type HI loops are often obtained with agglomerates or compacts of spheroidal particles of fairly uniform size and array. Some corpuscular systems (e.g. certain silica gels) tend to give H2 loops, but in these cases the distribution of pore size and shape is not well defined. Types H3 and H4 have been obtained with adsorbents having slit-shaped pores or plate-like particles (in the case of H3). The Type I isotherm character associated with H4 is, of course, indicative of microporosity. 

Other Industrial Applications. High pressures are used industrially for many other specialized appHcations. Apart from mechanical uses in which hydrauhc pressure is used to supply power or to generate Hquid jets for mining minerals or cutting metal sheets and fabrics, most of these other operations are batch processes. Eor example, metallurgical appHcations include isostatic compaction, hot isostatic compaction (HIP), and the hydrostatic extmsion of metals. Other appHcations such as the hydrothermal synthesis of quartz (see Silica, synthetic quartz crystals), or the synthesis of industrial diamonds involve changing the phase of a substance under pressure. In the case of the synthesis of diamonds, conditions of 6 GPa (870,000 psi) and 1500°C are used (see Carbon, diamond, synthetic). 

Silica and Alumina. The manufacture of Pordand cement is predicated on the reaction of lime with siUca and alumina to form tricalcium sihcate [12168-85-3] and aluminate. However, under certain ambient conditions of compaction with sustained optimum moisture content, lime reacts very slowly to form complex mono- and dicalcium siUcates, ie, cementitious compounds (9,10). If such a moist, compact mixture of lime and siUca is subjected to steam and pressure in an autoclave, the lime—silica reaction is greatiy accelerated, and when sand and aggregate is added, materials of concrete-like hardness are produced. Limestone does not react with siUca and alumina under any circumstances, unless it is first calcined to lime, as in the case of hydrauhc lime or cement manufacture. 

MicrocrystaUine Silicas. Various microcrystalline (cryptocrystalline) materials such as flint, chert, and diatomaceous earth are found ia nature (see Diatomite). These may arise from amorphous silica, often of biogenic origin, which undergoes compaction and microcrysta11i2ation over geologic time. 

W. Primak, Compacted States of Vitreous Silica, Gordon Breach Science PubHcations, New York, 1975, pp. 83—127. 

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